Copperable disazo dyestuffs



United States PatentO COPPERABLE DISAZO DYESTUFFS N Werner Bossard, Riehen, near Basel, Switzerland, and Paul Dussy, St-Louis, France, assignors to J. R. Geigy A.-G., Basel, Switzerland, a Swiss firm No Drawing. Application June 4, 1956 Serial No. 589,006

The present invention concerns metallisable disazo dyestufls as well as their copper complexes which are distinguished by excellent fastnessyto light and very good wet fastness properties of their coppered cellulose dyeings. It also concerns processes for the production of these new disaz-o dyestuffs as well as their use for the production of fast yellow to yellow-brown cellulose dyeings and, as industrial product, the material fast dyed with the aid of these dyestuffs.

In patent application Ser. No. 352,570 (now U. S. Patent No. 2,760,959, issued August 28, 1956), it has been shown that by coupling one mol of an unsulphonated 4.4'-di-acetoacetylaminodiphenyl compound with 2 mols of the same or with one mol of each of two different ocarboxy diazonium compounds of the benzene or naphthalene serieswhereby an aryl ureido radical must be present in at least one of the two diazo components-metallisable disazo dyestufis are obtained, the coppered cellulose dyeings of which have excellent wet fastness properties and are very valuable because of their greenish-yellow shades.

It has now been found that metallisable dyestuffs having excellent light and wet fastness properties are obtained if one mol of an azo component of the general Formula I y1 1 z- Y= (I1 iscoupled in any order desired with one mol of a diazonium compound of the general Formula II ('JOCtH and with one mol of.a diazonium compound of the general Formula III H (IV) In these formulae: 7

A represents an aromatic radical of the benzene or naphthalene series which contains at least one acid, water solubilising group,

Ph, and P112 represent the same or difierent p-phenylene radicals which may be substituted,

Py, and Py represent the same or difierent radicals of 5-pyrazolones which are linked with Ph in the 1-posi- 2,829,141 I Patented Apr. 1, 1958 X representsthe direct linkage or a divalent bridging member containing carbon, and

R represents an aromatic radical of the benzene or naphthalene series which contains in the o-position to the azo linkagea group capable of forming the metal complex and which also can represent the grouping COOH Advantageously such divalent bridging members are used which favour the substantive properties of the end products; thus, for example, the vinyl group, the carbamide and ureido groups, a 4.4'-divinyl diphenyl urea group, a diamide group or an aliphatic, aromatic or heterocyclic, polybasic acid, such as, e. g. fumaric acid, terephthalic acid or cyanuric acid. v

The pyrazolone nuclei can be substituted in the 3-position by aryl and preferably alkyl groups such as, e. g. the methyl group; and the p-phenylene radicals represented by the symbols Ph and Ph can intheir turn have, e. g. halogen atoms such as chlorine;"alkyl groups such as, e. g. the methyl group; carboxylic acid or sulphonic acid groups, preferably in the meta positions in regard to X.

The following can be named as examples of groups of dipyrazolones usable according to the present invention.

Compounds of the general Formulae l to 5 wherein Py, and Py have the meanings given above:

Pyl Py:

wherein Y represents hydrogen or, e. g. chlorine or. a methyl, methoxy, carboxyl or sulphonic acid group,

I Py CH=CH Pyfl '1 0.11 our wherein Z represents, e. g. CO, the cyanuric acid radical or a divalent radical of a dicarboxylic acid such as fumaric acid or terephthalic acid,

wherein Z has the meaning given above.

Some of such dipyrazolones are already known or can beobtained by known" methods from known components,

e. g. by combining aminophenyl or aminodisulphonic acid stilbenyl' monopyrazolones with dihalides Hal-Z-Hal, wherein Z has the meaning givenabove, for example with phosgene, fumaric or terephthalic acid dichloride or:

cyanuric acid chloride, the third halogen atom of the latter advantageously being replaced by a primary or secondary amino group.

The dipyrazolones usable according to the present in-v vention can be asymmetrical or symmetrical both with regard to the two p-phenylene radicals Ph, and Ph or the bridging member. However, it is of advantage to use those in which both the pyrazolone nuclei as well as the p-phenylene radicals are identical. such as, e. g. occurs in the 4.4-bis-[3methyl-S-oxo-pyrazolinyL 1 )]-diphenyl urea or in thev 4.4'-bis-[3-methyl-5-oxo-pyrazolinyl-(1)]-stiltion and linked in 'the4-position to the azo group; bene-3.3'-disulphonic acid. Dipyrazolones of the diphenyl series have proved to be particularly advantageous, whereby 4.4'-bis-[3-methyl-5-oxo-pyrazolinyl-(1)]-diphenyl unsubstituted in the diphenyl radical is of particular importanceboth because of its more easy accessibility as well as with regard to the good properties of the end products obtained therewith.

Diazo components of the general Formula II are already known. Amino compounds of the benzene and naphthalene series which contain at least one acid, water solubilising group of the general formula A-NH can be used to produce them. Examples are: 3- or 4-aminobenzene-l-sulphonic acid or carboxylic acid, 2-methoxy,

2-chloroor Z-methyl- 5-aminobenzene-l-sulphonic acid,

4-chloro, or 4- or 6-methyl- S-aminobenzene-l-sulphonic acid, 3.5-dimethyl-2-aminobenzene-l-sulphonic acid, 5- amino-Z-hydroxybenzene-l-carboxylic acid, S-amino-S- methylor 3-sulpho-2 hydroxybenzene-l-carboxylic acid, 'l-aminonaphthalene-4- or -5- or -6-sulphonic acid, 1- aminonaphthalene-3.6- or -3.8- or -4.8-disulphonic acid, 2-aminonaphthalene-4.8-, -5.7-or -6.8-disulphonic acid, 2-(4'-aminophenyl)-6-methyl-benzthiazole-5- or -7- sulphonic acid.

The usual diazotised o-hydroxy or o-carboxy amino compounds of the benzene and naphthalene series are usable in the process according to the present invention as diazo components of the general Formula III. For example alkyl sulphonyl-o-aminophenols can be used as o-hydroxyarnino compounds, such as 2-amino-4- or -5- methyl sulphonylor -ethyl sulphonyllhydroxybenzene as well as further substituted derivatives thereof, for example nitrated derivatives. Then Z-aminophenol sulphonic acid amides, e. g. 1-hydroxy-2-aminobenzene-4- or -5-sulphonic acid amide, or o-arninophenol sulphonic acids such as 1-hydroxy-2-aminobenzene-4-sulphonic acid, 1-hydroxy-2-aminobenzene-6-sulphonic acid or further substituted derivatives of the latter such as for example 4-nitroor 4-chloro- 2-amino-l-hydroxybenzene-G-sulphonic acid or 4- or 6-acetylaminoor -benzylamino-2- amino-l-hydroxybenzene-6- or -5-sulphonic acid and also 1.2-diazoxide naphthalene-4-sulphonic acid and 6-nitro- 1.2-diazoxide naphthalene-4-sulphonic acid can be used. The following for example can serve as o-aminocarboxy compounds: Z-aminobenzene-l-carboxylic acid, 2-amino benzene-1.4- or 1.6-dicarboxylic acid, Z-amino-l-carboxybenzene-4- or -5-sulphonic acid and the corresponding sulphonic acid amides, dialkylamides, ethanolamides etc., -1-aminonaphthalene 2 carboxylic acid, Z-aminonaphthalene-3-carboxylic acid and 5 acylamino 2 amino benzoic acids such as, e. g. the S-acetylamino-Z-aminm benzoic acid. Possibly however, such o-carboxy diazonium compounds are used which also correspond to the general Formula II and in particular those which are identical to the first diazo component and which lead to symmetrical disazo dyestuffs according to the invention which are produced in a simple manner.

CHrC=N The diazonium compounds of the general Formulae II and III are coupled with the dipyrazolones of the general Formula I in aqueous medium, if necessary in the presence of organic bases such as pyridine or homologues thereof.

Disazo dyestuffs according to the invention which contain at least one grouping -NHZ-NI-I- can also be produced by reacting an amino monazo ,dyestuff of the general Formula V COOK and an amino monoazo dyestuff of the general Formula wherein N represents 0 or 1, Q and Q represents the same or different, possibly substituted p-phenylene or styrylene radicals, and the other symbols have the meanings given under Formula IV above, with one mol of functional acid derivatives corresponding to the radical Z, of which examples have already been given in the passage regarding the production of the dipyrazolones.

The disazo dyestuffs obtained by the above methods are yellow to yellow-brown powders which dissolve well in hot water, possibly with the addition of inorganic salts having an alkaline reaction such as sodium carbonate, sodium phosphates or polyphosphates. They dye cellulose fibres by the usual methods in full yellow to yellowbrown shades.

The dyeings are treated in the dyebath or in a fresh bath with agents giving otf copper. As such, for example copper sulphate or copper acetate can be used, the treatment being performed in a neutral to weakly acid medium. It is also possible to use copper compounds which are stable to alkalies such as are obtained, e. g. on reacting copper sulphate with sodium tartrate in a soda-alkaline bath. The shade of the cellulose dyeing is altered to only an inconsiderable extent by these after treatments with agents giving off copper but the wet and light fastness properties are considerably improved.

If desired, the disazo dyestuffs usable according to the present invention can be treated in substance with agents giving off copper. Cellulose fibres dyed with such copper containing dyestuffs are distinguished by their excellent fastness to light.

The following examples illustrate the invention without limiting it in any way. Parts are given as parts by weight and the temperatures are in degrees Centigrade. The relationship of parts by weight to parts by volume is as that of kilogrammes to litres.

Example I 70.2 parts of 4-aminodiphenyl urea-3-carhoxylic acid- 4'-sulphonic acid are dissolved in 700 parts of water with 16 parts of caustic soda, the solution is mixed with 13.8 parts of sodium nitrite and diazotised by the quick addition of 72 parts of concentrated hydrochloric acid at 510 C. 12 parts of sodium bicarbonate are sprinkled into the lemon yellow suspension of the diazonium compound and a 20-25 warm solution consisting of 34.6 parts of l.l'-(4".4-diphenylene)-di-[3-methyl-pyraz clone-(5)], 500 parts of water, 8.4 parts of sodium hy droxide and 20 parts of sodium carbonate is added within one hour. After 3 to 4 hours, the dyestutf suspension is warmed to -65 2.5% of sodium chloride, calculated on the volume obtained, are added and the dyestutf of the formula:

is filtered off. The dried dyestutf is a yellow-brown powder which dissolves in water and in concentrated sulphuric acid with a yellow colour. It has good drawing power onto cellulose fibres which, when after coppered, are dyed in pure yellow shades which have excellent fastness to light and good wet fastness properties.

If instead of 70.2 parts of 4-aminodiphenyl urea-3carboxylic acid-4'-sulphonic acid, the same number of parts of 4-aminodiphenyl urea-3-carboxylic acid-3-sulphonic acid, 86.2 parts of 4-aminodiphenyl urea-3-carboxylic acid-2'.5'-disulphonic acid, 73.0 parts of 2- or 4'-methyl- 4-aminodiphenyl urea-3-carboxylic acid3-sulphonic acid, 77.1 parts of 2'- or 4'-chloro-4-aminodiphenyl urea-3- (v) 7 carboxylic acid-3'-sulphonic acid, 75.8 parts of 2.4'-di- -.5 "6 methy1-4-aminodiphenyl ufea-S-carboxylic acid-6'-sulid-3'-sulph0nic acid and neutralised with sod um tphonic id, 322 parts f 4- i .4'- d i h 1 bonate is poured mto this solution within one. hour. The ure a'-3.3-dicarboxylic acid-5'-sulphonic acid, 66.2 parts s 1s q t after hours: .T dy f 4 i 4' x asgdi'c bd li stufli formed is salted out with 2.5% of sodium chloride, acid. 62 parts of 4 aminodiphenyl urea "5- calculated on the volume obtained, filtered ofi, washed dicarbogyfic acid 80 2 parts of with diluted sodium chloride solution and dried.

naphthyl urea-3-carboxylic acid-4-sulphonic acid, 96.2 It Is a yellow-brown powder which dlssolves m hot h 11 hth l 3 b water with the addition of sodium carbonate with an parts of 4'ammop y urea oxy orange colour and in concentrated sulphuric acid with acid'3"-s"disulphonic acid 9 :2 P f 9 9 f f 10 a yellow-brown colour. The after-coppered dyeings on 3 P Y urea-3'carboxyllc cellulose fibres are reddish-yellow and have excellent sulphonic acid are used,'then dyestuifs with similar full, fastness to light.

yellow shades and properties are obtained. I i In the free form, the dyestuif corresponds to the formula:

NH.CQ-N N=N- =0 \O=C-N=N -NH-CO.NH

om OOH H H00 0.11

Example 2' I In the above example, if instead of 40.4'parts or the I A. 40.4 parts of the dipyrazolone of the formula: dlpyrazoloneof the formula: 1 CH C=N N=C-OH 0H o=N N=OCH I r /N NH-OO-NH N\ p v /N NH-OO-NH N\ H=o c= H OH=C c= H a in, e... a a.

are dissolved in 500 parts of water with 8 parts of sodium p 1 i hydroxide and 40 parts of sodium carbonate are added. the corresponding number of parts of one of the dipyraz- A diazoniurn salt dispersion produced by known methods olones given below are used, then similar dyes'tufis with from 70.2 parts of 4-aminodiphenyl urea-3-carboxy'lic 5 the same properties areobtained. I

same

107.0 m Oil -Ou h? ample l and neutralised with sodium bicarbonate. This a suspension is poured within one hour into a solution of 18.9 parts of 1-(4-aminophenyl)-3-methyl pyrazolone- (S) in 250 parts of water, 4 parts of sodium hydroxide and 20 parts of sodium carbonate. The coupling is complete after 3 hours. The monoazo dyestuff formed is precipitated with sodium chloride, filtered OE and then again dissolved in 1000 parts of 4045 warm water. Phosgene is slowly introduced into this solution while keeping the pH value constant at 7.5-8.0. As soon as no more free amino group can be traced, the azo dyestufl formed is precipitated with sodium chloride, filtered off, washed with diluted sodium chloride solution and dried.

It is chemically identical to the disazo dyestuif de; scribed in paragraph A and it has the same shade as well as the same excellent fastness properties.

Dyestufis withsimilar properties are obtained if the phosgenefis replaced by fumaric acid dichloride, fumaric acid dibromide, maleic acid, mesaconic acid, chloroor bromo-fumaric acid or terephthalic acid dichloride, or if 1 mol of cyanuric acid chloride is condensed first with 2 mols'of the monoazo dyestuff described above and then with 1 mol of aniline.

Example 3 73.0 parts of 4-methyl-4-aminodiphenyl urea-S-carboxylic acid-3'-sulphonic acid are diazotised in'the usual way and then neutralised with sodium carbonate whereupon 60 parts of sodium bicarbonate are added. An alkaline solution of 53.2 partsof the dipyrazolone of the formula:

dipyrazolone of the formula:

the corresponding number of parts of one of the dipyrazolones listed below are used, then dyestufis with similar properties are obtained.

40.4 parts CHrC=N rho-0H;

/N NH-CO-NH N\ GIL-.0 c= H on I:

41.5 parts CHzC-=N N=o-om H OH 37.4 parts CHHC=N Mic-om 011:0 0:03 2) H; CH; I

H OH

43.4 parts OEh-C N N=o-om 011:0 C=CH 00H 00011 A on H 40.6 parts 03.43:: N=C-CH:

CH=C o: H 1 cm on, 4) OH H 38.9 parts cares-1N N=C-CHI If, in the above example and its variations with regard to the dipyrazolone, instead of 730 parts of 4'-methyl-4- aminodiphenyl urea-S-carboxylic acid-3-sulphonic acid, 70.2 parts of 4-aminodiphenyl urea-S-carboxylic acid-4'- sulphonic acid are used, then similar dyestuffs with the same good properties are obtained.

Example 4 water,-8-'.4 parts of sodium hydroxide and 20 parts of sodium bicarbonate. On completion of the coupling, a further 20 parts of sodium bicarbonate are added and the diazonium compound from 18.7 parts of 4-methyl ass-91 9 sulphonyl- Z-amino-l-hydroxybenzeneis poured inwithin If, instead ot the 70.2 parts of. 4;.aniinodiphenyl. urea- ;l'liour; The dyestufi formed of the-formula; 1 3- carbo7iyli c acid j4' -sulphonicj'acid, 86.2 part f 4 00H H is separated in the warm with sodium chloride, filtered aminodiphenyl urea 3 carboxylic acid-2'.5-disulphonic olfand dried. It is a yellow-brown powder which disacid, 73.0 parts. of. 2'-, or 4'-methyl-4-amino-diphenyl solves in water and in concentrated sulphuric acid with urea-3'-carboxylic'acid-3-sulphonic acid, 80.2 parts of a yellow colour. It dyes cotton, staple fibres, viscose, 4-aminophenyl-1.1'-naphthyl urea-3-carboxylic acid-4'- hemp and jute fibres, when after-coppered, in yellow sulphonic acid or 96.2 parts of"4-aminophe'nyl-l.l"- shades which have excellent fastness properties. naphthyl urea-3-carboxylic acid-3'.8'-disulphonic acid are If in the above example the 18.7 parts ,of 4-methyl used, then similar dyestuffs with the same properties are sulphonyl-2-amino-1-hydroxybenzene are replaced by the obtained. a number of parts of a diazo component given in the fol- Example 6 1322i rig then dyestufls having the Properties given 2 parts of the dyestufi obtained according to Example Diazo component coupled with the monoazodye- Dye- Numstuff from 35.1 parts of 4-amino-3-carboxydl- Resulting dyesturlzP=color of powstuff her of phenyl urea-4-sulphonio acid and 34.6 parts of. er S=shade of dyeing after treated No parts 1.1- (4.4- diphenylene)-di-[3-methyl-pyrazowith copper salts.

lone-(5)] 18. 7 5-methyl sulphonyl-Z-amino-l-hydroxybenzene-... P=orange; S=reddish yellow.

20. i 4-ethyl sulphonyl-Z-amino-l-hydroxybenzene Do.

20.1 5-ethy1sulphonyl-2-amino-1-hydroxybenzene. Do.

18. 9 l-hydroxy-2-amlnobenzene-4-sulphonic acid vP=yellow; S=greenish yellow.

18.9 l-hydroxy-z-aminobenzene-6-sulphon1c acid... Do. g

22. 4 4-eh1lgro-2-aminol-hydroxybenzene-G-sulphonic P=brown; S =yellowish orange.

23. 4 4-nitro-2-amino-l-hydroxybenzene-B-sulphonic acid. 7 Do.

25.0 1.2-diazoxide-naphthalene-dr-sulphonle acid P=red-brown; S=orange.

I 29. 5 6-nttro-1.2-diazoxide-naphthaIene-4-sulphonicacid Do.

13.7 Z-amino-l-carboxybenzene P=yell0w-brown; S=greenish yellow.

21.6 Z-amino-l-carboxybenzene-4-s1flphonamlde. P yellow-brown; S=yel1ow.

2i. 6 2-amlno-l-carboxybenzeneS-sulphonamide. vDo.

19.4 fi-acetylammo-2-amino-1-carboxybenzene P' yellow-brown; S=greenleh yellow..

18.7 2-aminonaphthalene-3cerboxylie acid- P=brown; S=orange.

Example 5 5 are dissolved 1n 3000 parts of water and 2 parts of sodium carbonate. 100 parts of cotton are entered into parts p q y 3 y c dthis dyebath at 40-45, the bath is farmed within 30 P acld dlazotlsed as descrlbed in minutes to 90-95, 30 parts of sodium sulphate are added ample neutralised with Sodium carbonate and then 60 and dyeing is performed for another 45 minutes at this parts of sodium bircarbonate are added. An alkaline t t Af thi i h dyed goods are i d solution of 53.2 parts of the dipyrazolone of the formula: ld i the usual way and dried. The cotton is dyed cHl-0=N N=OCH1 in reddish-yellow shades which have very good fastness l NQoH=oH3 to light and good wet fastness properties.

H=C c H (5 0m 0m 7 A Example 7 g H I n 2 parts of the dyestutf obtained according to Example" is added within 30 minutes. 1 are dissolved in a dyebath containing 3000 parts of On completion of the coupling, the dyestuff formed is water and parts of sodium carbonate. 100 parts of cotseparated withsodium chloride at -809, filtered otf and ton are entered at 40-50, the bath is warmed within again dissolved in 2500 parts of water at -85'. 400 30 minutes to -95 30 parts of sodium sulphate are parts of a copper oxide-ammonia solution, which contains added and dyeing is performed for 45 minutes at this 50 parts of crystallised copper'suplate and parts of ,7 "temperature. After-this time, the dyed goods' are rinsed concentratedaqueous ammonia, are added and the whole 60 cold and after-treated in a fresh bath with 2 parts of is stirred for some time at this temperature. The copper crystallised copper sulphate in 2000 parts of water and complex formed is precipitated with sodium chloride, 2 parts of 30% acetic acid. The after-treatment is perfiltered off and dried. It is a yellow-brown powder formed at 70.for 30 minutes. The goods are rinsed which dissolves in water and in concentrated-sulphuric and'dried in the'usual way. The pure yellow cotton acid with a yellow colour and which draws verywell 65 dyeing has excellent fastness properties. onto natural and regenerated cellulose fibers. The red What we claim is: dish yellow dyeings have excellent 'fas'tnes's'to light and H I 1. A copperable disazo dyestutf corresponding to the in addition have good wet fastness properties. general formula:

CHI (1113 N=C COOH A-NH-O 0-NH N- Nc=0 C=CN=NR H AH L were, 1'41 "11 12 an aromatic containing at \illier'ein Dlrepresents a sulphophenyl radical, Q reprelawman-member darbocyclicnuclus and at most sents a mononuclear radical of the benzene series, and two such nuclei condensed with one another and which Y represents a metallisable group in o-position to the contains an acid water solubilising group, X represents azo group 'selected from the group consisting of OH and a carbon containing bridging member, 71 is one of the 5 COOH. integers O and 1, R represents an aromatic radical se- 3. A copperable disazo dyestufi of the general formula:

?H; CH CODE {3:}:\ C

' O a== n OH OH Y lected from the group consisting of radicals of the wherein D represents 'a sulphophenyl radical, Q reprebenzene and naphthalene series, Yrepresents a metal- 15 sents a mononuclear radical of the benzene series and lisable group in o-position to the azo group selected Y represents a metallizable group in o-position to the azo from the group consisting of OH and COOH. group selected fromthe 'group consisting of OH and 2. A copperable disazo dyestutf corresponding to the COOH.

general formula:

CH: CH: coon I DNH-C 0-NH N=N-l=(3 crc -Nrn-q 4. A copperabledisazo dyestutf of the formula: CHa-(L- N Nee-om I OC I Hms-ONH-o o-NHQN=N-o=o C=C-'N=N-: NH-O 0-NHOS 0,11

5. A copperable disazo dyestufl of the formula: (Em-om N=CCH:

COOH

6. A copperable disazo dyestutf of the formula:

References Citedin the tile 0t this patent UNITED STATES PATENTS 7 Re. 23,380 Widmer Jun'e"12,'195 1 2,760,959 Bossard et al AugPZS, 1956 

1. A COPPERABLE DIAZO DYESTUFF CORRESPONDING TO THE GENERAL FORMULA: 